Journal of Physical Chemistry A, Vol.120, No.26, 4447-4454, 2016
Extension of Structure-Reactivity Correlations for the Hydrogen Abstraction Reaction to the Methyl Radical and Comparison to the Chlorine Atom, Bromine Atom, and Hydroxyl Radical
Recently, we presented structure-reactivity correlations for the gas-phase rate constants for hydrogen abstraction from sp(3)-hybridized carbon by three electrophihc radicals (X-center dot + HCR3 -> XH + (CR3)-C-center dot; X = Cl-center dot, HO center dot, and Br-center dot); the reaction enthalpy effect was represented by the independent variable Delta H-r and the "polar effect" by the independent variables F and R, the Hammett-Taft constants for field/inductive and resonance effects. Here we present a parallel treatment for the less electronegative CH3 center dot. In spite of a limited and scattered database, the resulting least-squares fit [log k(437)(CH3 center dot) = -0.0251 (Delta H-r) + 0.96(Sigma F) - 0.56(Sigma R) - 19.15] was modestly successful and useful for initial predictions. As expected, the polar effect appears to be minor and its directionality, i.e., the "philicity" of CH3 center dot, may depend on the nature of the substituents.